Production of chemical changes by oscillatory discharge.



E. F. NOR'THRUP. PRODUCTION OF CHEMICAL CHANGES BY OSCILLATORY DISCHARGE.

ARPLICATION FILED JULY 13. I917.

Patented Mar. 18,1919.

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E w ptwaoo UNITED STATES PATENT OFFICE.

EDWIN F. NORTHRUP, OF PRINCETON, NEW JERSEY, ASSIGNOR TO THE AJAX METAL COMPANY, OF PHILADELPHIA, PENNSYLVANIA, A CORPORATION OF PENNSYL- VAN 1A.

PRODUCTION OF CHEMICAL CHANGES BY OSCILLATORY DISCHARGE.

To all whom it mag concern:

Be it known that I, ,Enwm F.-NoR'rHRU1 a citizen of the United States, residing at Princeton, in the county of Mercer and State 5 of New Jersey, have invented a certain new and useful Production of Chemical Changes by Oscillatory Discharge, of which the following is a specification.

The purpose of my invention is to use oscillation current discharge for producing chemical change, 'which may be either chemical synthesis or chemical dissolution.

A further purpose is to apply to the art of chemical combination or dissociation an 16 agency new to that art for promoting or causing the change.

A further purpose is to provide oscillation current discharge in a substantially closed compartment so that the atmosphere can be 20 controlled and to bring the materials,

whether solid, liquid or gaseous, whose combination or dissociation is sought, as close to the discharge gap as possible.

A further purpose is to make a liquid one of the-two electrodes between [which oscillatory discharge takes place where the liquid is to take part in an intended synthetic combination or chemical dissociation process.

A further purpose is to discharge oscillatory current as close as possible to the surface of a liquid whose elements are to enter into, affect or be subject to chemical change.

A further purpose is to-pass an oscillation 85 current discharge between mercury and a solid electrode in the presence of a gas capable of combination with mercury and 1 illustrate my invention by a special application to the use of air as the atmosphere of the gap, and the fixation of nitrogen in atmospheric air.

A further purpose is to perform my operations in an atmosphere preferably at or near the atmospheric pressure, where possible, to avoid the difiiculty of attaining and maintaining different pressures; contemplating, however, the use of special pressures where-the chemical change sought is facilitated by thun. 1

A further purpose is to obtain fixation of atmospheric nitrogen by oscillatory dis charge between a solid electrode and a liquid which combines \Wllll'l the nitrogen of the air in the discharge.

Specification of Letters Patent.

.A further purpose to secure abruptness of discharge and of discharge in the circuit containing the gap and form as regular impulses as possible.

A further purpose is to utilize the liquid which is to enter into the combination to maintain high uniform voltage of discharge.

A further purpose is to use the favorable characteristics of a mercury discharge gap to standardize and control the discharge impulses even when the discharge utilized for chemical operations does not take place in the presence of the mercury. 7

Further purposes will appear in the specification and in the claims hereof.

I have preferred to illustrate my invention by but three forms thereof, selecting forms whichv are typical of the use as an electrode of a liquid furnishing part of or catalytically improving chemical operations; discharge between electrodes over or through the sur ace of such liquid; and discharge in the presence of gases which are to be combined or chan ed.

Figures 1 an 2 are partly sectional, partly diagrammatic views of two forms of apparatus for carrying out my invention.

Fig. 3 is a fragmentary side elevation showing other forms of apparatus for carrying out my invention.

In the drawings similar numerals indicate corresponding parts.

My invention relates both to processes and to the apparatus for carrying them out.

Since my invention may be applied both in synthesis and in dissociation, I shall refer to these generally as chemical changes.

Whether the chemical change is intended to take place in one type of gap illustrated or another, I find it advantageous to maintain a high uniform voltage in the circuit and to prevent maintained arcs between the electrodes. For this reason I show a desirable form of discharge gap in each of my figures, which gap is located .within a cham- Patented Mar. 18, 1919. v

Application filed July 13, 1917. Serial No. 180,288.

g and uniform voltage her and automatically maintains this desirable voltage and prevents maintained arcs by shutting off the lower voltage discharges, obtaining the benefit of the high negative electrode resistance of mercury in both directions of impulse travel with the resultant benefit in regulation and a sharp, abrupt, clear discharge.

- character of impulse denser 6 is charged.

The form of'ga illustrated is not intended to be claimed y me in this application except in connection .with the application of its dlscharge or a to effect or assist chemical change, as it is described and claimed by me as a gap in a copendin application for dischar e ap,Serial N o. 1%5518, filed June 18,, 191 ts discharge is here valuable for the efl'ect which it produces directly upon substances about it and also because ofthe strong andsteady maintained by it in other gaps in circuit with it.

As compared with such a. structure as is shown in Swedish Patent N 0. 24,010 to Mosciki, my invention rent as the main source ducing chemical change.

Describing Fig. 1, then as one form of apparatus and connections b which chemical changes can be brought about through the agency of oscillatory discharge, I show at A A, an alternating current supply of any desired phase, here single phase, and which may have any commercial voltage and frequency. I have successfully used a voltage of 220, stepped up to 8,000 or 10,000 volts, at a frequency of cycles.

Where the voltage differs from that desired for.charging the condenser in the oscillatory circuit a transformer 5 is used,

111 whose secondary, in that case, the con- It is discharged through a gap 8 and the inductance 7. The discharge gap is used in Fig. 1 for the double purpose of regulating and controlof current for proling the character of discharge and of causing the chemical change, here a synthetic change. The desired combination takes place. between the liquid electrode used and the atmosphere about the discharge.

In this il ustration I have shown a much more complicated and refined form of mercury-electrode discharge gap than is required to obtain 'good oscillations or to combine the mercury with the atmosphere chemically; illustrating a common pool for both of the solid electrodes, where independent pools and containers are entirely practicable, showing outsidecooling means and supplying other detail which is convenient and desirable but not essential in carrying out even this form of my process.

The cover 10 is important because it makes possible complete control of the atmosphere of the gap within. the compartment I 11, restricts the scattering of the mercury,

quiets the gap and prevents undue scattering of the chemical compound formed. The mechanical subdivision and dispersion of the mercury by reason of the disruptive character of the dischar e is helpful in increasing the quantity oi mercury which is exposed to the action of the discharge.

Both the pot 9 and the cover are desirably discharge affected thereby uses the oscillatory cur-,

-or gas desired which cannot y droppers of the type shown at 19.

made of material which is electrically nonconductin of which one of'the best materials for t e purpose is porcelain.

The solid electrodes 12 are preferably tipped with non-corrosive non-plttin tips 13 for which I have found graphite su table. Any material will serve this purpose which either does not affect the chemical change made or desirably enters into or assists the process.

The solid electrodes are shown as pro vided with flanges 14 so that they may be rested in place, and as threaded at the tops for nuts 15 by which they may be connected in the circuit; 7

In order to reduce the danger of short circuiting, the solid electrodes are assed throu h. sleeves 16, likewise prefera ly of porce ain, or other vitreous material. At the temperature at which such gaps no mally operate the mercury scattered by the discharge is dissipated by the surface upon which it falls.

Each of the tips 13 is to a pool of mercury 17, here shown as common to both electrodes. Obviously either of the members may be adjusted to vary the extent of the gap. I prefer to make the mercury level ad ustable and for that purpose show a pipe connection 18 by which the mercury ma be connected with a pool of mercur capa 1c of bodilyvertical movement as isclosed and claimed in the copending application previously referred to.

I show a dropper 19 for the purpose of feeding liquid or vapor into the space 11 about the discharge gaps, by which I. may contribute to placed in proximity or retard chemical action or' actions or change their character.

The outer casing 20 may be spaced from the pot 9 to provide air insulating space merely or to permit the use therein of a liquid or gas supplied from any suitable source, as through pipe 21. The liquid or gas may be used merely for cooling pur poses or ma be either solely or partially intended to eed gas (including vapor) into the space 11 as shown in Fig. 2, where the outlet 22 ma be used merely as a vapor outlet or may eed fluid through inlet pipe 23 and connection 24. An additional inlet 23 may be used to admit air or any solid, liquid be conveniently fed b All of these forms of inlet may be regulated, the regulations for the dropper 19 shown being as a conventional type used in feeding lubricating oil. -In the gap shown in Fig. 1, I have successfully tested air, illuminating gas, steam, alcohol, carbon dioxid, .water and poses.

toluene for various pur-- I have used ethyl alcohol with great success within the space between the pot and outer casing and'have found its vapor desirable in space 11 for'cooling purposes. It reduces the quantity of air available for combination with the mercury and, if in sufiicient quantity to keep the air out altogether, stops the synthetic combination. Other gases and liquids perform similar functions.

Within a discharge gap of which mercury forms one electrode, both air and steam atmospheres combine with the mercury to form desirable compounds. Certain proportions of both illuminating gas and alcohol vapor with air may be ignited or exploded by the discharge and this characteristic must be arded against.

In all oscilIa tion circuits there are two main ways in which energy is dissipated, namely, in the discharge, and in application to the intended use. In the circuits described (Fig. 1) energy is dissipated also in the chemical synthesis which takes place. There is a great increase in etliciency in mercury gaps such as shown in Figs. 1 and 2 where alcohol vapor displaces substantially all of the air in the chamber 11 as compared with the efficiency where the gap is surrounded by air. vapor is used almost no synthetic chemical change takes place, contrasting with considerable chemical change when air is freely admitted. Though part of the increase in efiiciency with alcohol vapor is due to beneficial cooling of the gap by the alcohol a considerable part of the efficiency increase is due to the saving of the energy expended in synthetic chemical change where the atmosphere is air.

In Fig. 2 in conjunction with 'my preferred discharge gap for maintaining high and uniform voltage of discharge and sharp, regular rupture of the circuit, I have shown a su plemental discharge gap intended for synt etic chemical operations or dissociation of chemical compounds alone, using some other liquid as the electrode. provided with a closure 26 so that the atmosphere within may be controlled and undue scattering of the liquid and of the chemical compounds produced may be prevented.

The interior 27 may contain any suitable gas or gases or liquid above the liquid electrode. A solid electrode 28, joined to the circuit at 29 is supported by the cover and insulated therefrom, as at 30, permitting the use of an electrically conducting material for the pot and cover, where desired.= Porcelain or similar non-conducting material having a vitreous surface would be advantageous here also.

The lowerpart of the pot is shown as holding a liquid electrode. The liquid or liqulds and the atmosphere will be selected with a Where the alcohol- The pot 25 is.

regularly fed into the pot and by which its height and the spacing of the gap between the electrodes,

may be controlled either by a supplemental. container of adjustable height or by other means. The gap is here adjustable by screwing the solid electrode up or down.

In the discharge gap 8, in Fig. 2 I show a liquid 38 floating on the surface of the mercury and dispersed by the discharge. It illustrates the use of two liquids with or without surrounding special atmosphere. The twoliquids can thus be chemically changed, as, for example, by being made to combineor combined with the atmosphere; or a lighter liquid may be finely distributed in and combined with an atmosphere with which the liquid electrode will not combine, or may be dissociated. I have dissociated water in this Way, both by floating it upon a mercury electrode, and by using it as an electrode.

In Fig. 3, the same kind of mercury gap used gaps to regulate and steady their discharges. Switch mechanism permits either or both of the supplemental gap devices 33 and 33 to be cut out of the circuit. Here again, another gap could be used instead of the one shown by me at 8, though with less advantage, and the use of any additional gap at 8 may be avoided where the character of the other gap or gaps used for the chemical operation sufficiently controls and maintains the voltage, character and rate of discharge required to accomplish the change sought. I believe that superior results are attained by using a mercury gap and that some chemical combinations or dissociations are rendered easy by it which would be difficult if not impossible, without the control of the voltage and the abruptness and regularity of discharge due to using the high negative electrode resistance of mercury.

In the gaps shown at 33 and 33 I provide solid electrodes 34 and 35, 36 and 37 between which the discharge takes place. In the gap 33 the discharge is arranged in suitable proximity to a liquid 38', intended to cooperate in the synthetic chemical combination to be formed or itself to be dissociated. The atmosphere at 39 about the discharge may be gas or vapor and a lighter liquid 38 may also be used. Obviously also, the presence of any of the liquids used by me may be desirablefor catalytic cooperation alone.

In the device shown at 33, no liquid is indicated and the synthetic change is intended to be effected between or Within gases or vapors alone. i In all my forms solid matter, preferably finely divided, and any fluid, whether liquid,

gas or vapor or any mixture "of these may be inserted through one or other of the inlets shown generically at 18, 19,23 and 32,.as may be required for the several operations.

The portion of the circuit shown in Fig. v 3 is intended to be connected sired oscillation circuit and may be connected with such a feeding circuit as shown in Figs. 1 and 2 by connecting the wires 40, 41 thereof to the remainder of the circuit at the points 40, 41 in these figures.

The devices shown in Fig. 3, connected in series for convenience of illustration, may be so used. In order to show their capability of independent use, I have illustrated jumpers 12, provided with switches 43 by which either or both of these may be cutout.

In operation, with the form shown in Fig.- 1, when there is free access of air, the dis charge causes the mercury to combine with the nitrogen and oxygen of the air, separately, forming a dark gray, almost black powder comprising a mixture of nitrate of mercury, Hg,(NO and the gray sub-oxid By the application of' of mercury, Hg O; gentle heat, the nitrate of mercury is made to yield N0 which, passedthrough water, gives nitric acid and the mercury is also'r'eleased from the oxygen, making the operation cyclic, so far as the mercury is concerned, in that all of the mercury is recov-.

ered.

The cooling use of vapor, as for example, alcohol vapor, about the gap, reduces the entire quantity of air present and consequently reduces the extent both of desirable production of mercuric nitrate and of the undesirable production of mercuric oxid. However, the formation of the undesirable sub-oxid of mercury may be reduced to advantage, without reducing the quantity of the mercuric nitrate by reducing the proportion of oxygen in the air. This may be done I by passing the air over hot coke, through the fractional distillation ofdiquid air, or by other well-known ways.

I have considered the use of alr as the atmosphere for the application of my inv vention to fixation of nitrogen because of the cheapness and ease of handling air even when it is desirable to reduce its oxygen content before use, and. because of the desirable voperation of both the'gap described and my process, herein sures.

Obviously, my invention will apply also to other mechanical mixtures of nitrogen, provided injurious gases be not present to suflicient extent to interfere with the combination sought. It is applicable also with pure nitrogen at atmospheric temperatures. As I have indicated at another point claimed, at atmospheric presin regard to other gases, the adaptability of my invention to use with gases at atmospheric pressures is viewed by me as a conwith any dedischarge gap electrodes cally changed by reason of the discharge.

2. Apparatus for chemical synthesis comprising a container, a solid electrode and a fluid electrode therein and a gas or vapor surrounding the electrodes and with which the fluid electrode will cooperate in the production of chemical compounds in combination with a source of high frequency electrical supply, applied across the space-between the electrodes to produce the chemical union.

3. Apparatus for chemical synthesis com prising a container, a solid electrode and a mercury electrode therein and air about the electrodes having a low oxygen" content as compared tothe nitrogen present in combination with a source of high frequency electrical supply, for causing the mercury and m'tro en to combine;

pparatus for chemical synthesis comprlsmg a solid electrode, a mercury electrode in proximity thereto, a container therefor admitting air-in combination with a source of high frequency electrical supply, crossing the gap between the electrodes for causing the mercury to combine with thenitrogen of the air.

5. Apparatus for effecting chemical! changes comprising a mercury discharge gap, a second gap in series therewith and material to be chemically imity to the second gap.

6. Apparatus for effecting chemical change comprising an oscillation discharge gap, a casing thereabout, within which'the material to be treated may be acted upon and-a second oscillation discharge gap giving character to'the discharges in the circuit.

7. In apparatus for chemical synthesis, and a plurality of fluids in proximity to the gap.

8. A pair of oscillation discharge gaps in series, one maintaining a high voltage of discharge and the other efl'ecting chemical changes.

9. A pair of oscillation discharge gaps in series, one producing strong and steady oscillations and the other applying the oscillations to effect chemical change.

changed in prox- 12. The process of fixation of nitrogen.

which consists in discharging an oscillatory current across a gap from or to a mercury electrode in the presence of a gas rich in uncom'bined nitrogen.

13. The process of fixation of nitrogen which consists in combining mercury and free nitrogen by means of electrostatic discharge.

- 14'. The process of fixation of nitrogen which consists in discharging an oscillatory current across a gap between a solid electrode and mercury in the presence of a mixture of air and another gas.

15. The process of fixation of nitrogen which consists in discharging an oscillatory current across a gap between a solid electrode and mercury in the presence of air and concurrently cooling he gap.

16. The process of fixation of nitrogen which consists in discharging an oscillatory current across a gap between a solid electrode and mercury in the resence of air and using alcohol to reduce t e temperature.

17. The processof synthetic fixation of nitrogen which consists in producing mercury nitrogen compound by the passage of oscillatory current between mercury and a solid electrode in the presence of air to cause union between the mercury and the nitrogen of the air and subsequently heating the mercuric nitrate.

18. The process which consists in passing an oscillatory current between mercury and a solid electrode in the resence of air to cause the mercury to combine separately with the nitrogen and with the oxygen of the air.

19. The process which consists in passing an oscillatory current between mercury and a solid electrode in the presence of air to produce combinations of mercury with nitrogen and with oxygen respectively and subsequently heating the resultant combinations to cause the evolution of nitric oxid, combining it with water to form nitric acid, and

returning the mercury to liquid form.

20. The process of production of nitric acid [which consists in passing oscillatory .electric current betweenmercury and a solid electrode in the presence of air to produce nitrate of mercury and subsequently treatin the resultant compound to produce nitric oxld and nitric acid, successively and to recover the mercury.

21. In the process of production of fixed nitrogen by passing an oscillatory electric current across a mercury and solid discharge gap producing mercuric nitrate and a mercury sub-oxid, the step which consists in preliminarily removing oxygen from the air about the gap.

22. The process of fixation of nitrogenwhich consists in the formation of a compound between mercury and nitrogen by passin oscillatory electric discharge across a gap etween mercury and a solid electrode in the presence of nitro en.

23. The process of Ex which consists in producing a mercury compound with nitrogen and a mercury compound with oxygen concurrently by the passage of an oscillatory current between mercury and a solid electrode.

24. The process of fixation of nitrogen which consists in producing a mercury compound with nitrogen and a mercury compound with oxygen concurrently by the passage of an oscillatory current between mercury and a solid electrode in the presence of air and relatively reducing the quantity of the mercury compound with oxygen by reducing the oxygen content of the alr,

25. The process of producing chemical change by the action of an oscillation discharge which consists in maintaining strong and steady oscillations by a discharge gap separate from the gap in which the chemical change is effected but in series in the same circuit with it.

26. The process of producing chemical change which consists in passing an oscillatory discharge through a liquid to disperse the latter and at the same time subject it to the action of the discharge.

27. The process of producing chemical change which consists in passing an oscillatory current comprising the main agent for producing chemical change, across a gap in thedpresence of the material to be dissociate 2b. The process of producing chemical synthesis which consists in passing an oscillatory current comprising the main agent for producing chemical change, across a gap in the presence of materials to be chemically combined.

29. The process of producing chemical synthesis which consists in passing an oscillatory current across a gap in the presence of fluid intended to enter into the synthetic combination and above the surface of a liquid adapted to affect the combination formed.

30. The process of producing chemical synthesis which consists in passing an oscillatory current across a gap in the presence of a plurality of gases adapted to enter into chemical combination, thereby bringing about the combination.

31. The process of producing chemical ation of nitrogen synthesis which consists in uniting fluids in chemical compounds by the production of an oscillatory discharge in the presence of the synthesis. which consists in subjecting to an oscillatory discharge comprising the main agent for producing chemical change; a plurality of materials vuhich affect the character ofa synthetic c mbination to be. formed. 35. The process of producing chemical synthesis which consists in subjecting to an oscillatory discharge the materials to be combined contained in one discharge-gap vessel connected in series with another discharge gap capable of producing and maintaining strong and Steady electrical oscillations. i

36. The process of producing chemical change which consistsin exposing a chemical combination to the effect of 'anoscillation current discharge comprising the main agent for produclng chemical change, for the'purpose of breaking the combination up into other combinat ons or its constituent parts. EDWIN F. N ORTHRUP. 

